JP3162169B2 - Recording material with antistatic properties - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001] The present invention relates to a recording material in which a sheet, ribbon or web carries an antistatic layer.

[0002] Low-conductivity resin-coated papers or films can become electrostatically charged by friction with dielectric materials and / or by contact with transport means that can be electrostatically charged, such as rollers. Is known. Charging easily occurs, especially in a relatively dry atmosphere.

[0003] Sheets, ribbons or webs made from hydrophobic resins or coated with such resins, for example polyester resins or cellulose triacetate, are commonly used as substrate materials or supports in recording materials. Such supports can be combined with other elements during the production of the recording material, for example during the coating or cutting stage, and during use, for example during the recording of information or (in the case of silver halide photographic materials) image processing or projection. Receive frictional contact. Particularly during winding or rewinding of the dried photographic film in a camera or projector, high friction occurs, creating electrostatic charges that can attract dust or generate sparks. In unprocessed photographic silver halide emulsion materials, sparking creates unwanted exposure marks and degrades image quality.

In order to reduce the electrostatic charge of a sheet or web containing a hydrophobic resin layer or a support without impairing transparency,
It is known to provide coatings formed from or incorporating ionic compounds, such as antistatic high molecular weight water-soluble polymer compounds having ionic groups at many intervals in the polymer chain [e.g., London. The Focal Press196
Published 6 years, GF Duffin, Photographic Emulsion
Chemistry, p. 168 and U.S. Pat. No. 4,301,240]. Examples of polymers used for this include salts of polyacrylic acid, salts of polystyrene sulfonic acid and copolymers containing quaternary ammonium groups. However, the water-soluble antistatic component will not remain when the processed sheet or web material has been subjected to aqueous processing, such as in the processing of photographic silver halide emulsion materials.

For example, water-soluble ionic polymers containing protonated or quaternized amino groups provide good antistatic properties prior to aqueous processing, but the dry processed photographic silver halide emulsion materials are dried. It does not provide a satisfactory conductivity to prevent electrostatic dust suction of the resin film support . This is because the polymer is leached from the coated material during the aqueous treatment.

US Pat. No. 4,301,240 discloses a cross-linking method for improving mechanical properties and antistatic properties in a dispersed form in a hydrophilic colloid binder layer such as a gelatin-containing layer of a photographic gelatin-silver halide emulsion layer material. Photographic materials using acrylic or methacrylic acid polymer salts are described.

In US Pat. No. 4,677,050, further cross-linked carboxylate-containing copolymers as defined by the general formula (I) are used to improve the antistatic properties of hydrophilic photographic silver halide emulsion materials. It has been added to the coating composition in a dispersed form in water.

The advantages of the use of the dispersed polymeric carboxylate salts derive from their resistance to diffusion, low swelling power and their properties which do not affect the viscosity of the gelatin-containing coating composition. The dispersed crosslinked polymeric carboxylate salts remain diffusion resistant due to their insolubility in the hydrophilic colloid layer under the pH conditions encountered in photographic processing solutions to process the imagewise exposed silver halide emulsion layer material. Will remain.

According to the present inventors, the alkaline metal salt of the crosslinked carboxylate polymer improves the conductivity of the hydrophilic colloid layer, but the conductivity is significantly reduced in an aqueous medium having a pH of less than 5. Was found experimentally. Since the acid fixer, which simultaneously acts as a stop bath for alkaline development, has a pH of 5 or less, for example in the range of 5 to about 4, an improvement in the sharp drop in conductivity at said low pH values must be found. .

According to the present inventors, it has been experimentally demonstrated that latexes based on crosslinked polymers containing quaternary ammonium salts after treatment in an alkaline aqueous treatment liquid have lost many of their conductivity enhancing properties. Was found.

It is an object of the present invention to provide a hydrophilic colloid incorporating an ionically crosslinked copolymer in which the copolymer provides satisfactory conductivity to the recording material, even after wet treatment at a pH lower than 5. It is to provide a recording material comprising a binder layer and a sheet, ribbon or web support.

[0012] Other objects and advantages of the present invention will become apparent from the following description and examples.

According to the present invention, the recording material has antistatic properties.
Incorporates ionic copolymer applied in the form of an aqueous dispersion to be applied
Material comprising a coated sheet, ribbon or web support layer
In the above, the ionic copolymer is a crosslinked addition copolymer
A body, ionically crosslinked addition copolymer, (1) acrylic and / or methacrylic acid aliphatic ester groups
At most 19 mol% of the repeating unit (2) a repeating unit which is an acryl and / or methacrylic acid base;
Position most 30 mol%, (3) a polyfunctional ethylenically unsaturated addition polymerizable cross-linking monomer
(1) 10 to 10 mol% of a repeating unit which is a copolymer , and (4) a carboxylic acid originally present in the repeating unit of the copolymer.
The reaction of the acid-base and propane Surt down or butane sultone
Iteration unit less containing a sulfonate group obtained through
A recording material characterized by comprising at least 50 mol%
Provided.

The ionically crosslinked addition copolymer used according to the present invention can be easily dispersed in an aqueous medium, does not increase the viscosity of an aqueous gelatin solution, does not aggregate gelatin, and has a matte effect on gelatin coating. do not do. In addition, the present invention
The ionic cross-linked addition copolymer used is 1 to 10 mol
Using a crosslinkable monomer capable of addition-polymerizable ethylenically unsaturated
It is water-insoluble because it is manufactured by

FIG. 1 shows the surface resistivity, expressed as a logarithmic value (logR _s ), versus the pH of a gelatin layer containing a prior art crosslinked carboxylate copolymer and a crosslinked sulfonate copolymer according to the present invention, respectively. The plotted graph is shown.

FIG. 2 shows the surface resistivity (log R _s ) of the gelatin layer containing the sulfonated cross-linked copolymer versus the increasing conversion (in mole%) of carboxylate groups to sulfoalkyl acrylate groups. It is a graph plotted. Surface resistivity measurements are performed on the exposed photographic silver halide emulsion layer after the layer has been subjected to an aqueous treatment (see Example 1).

According to a preferred embodiment for improving the antistatic properties of the hydrophilic colloid layer, the ionic crosslinked addition copolymer is incorporated therein in the form of an alkali metal salt, for example, as a potassium salt.

[0018]

[0019]

Suitable polyfunctional ethylenically unsaturated monomers which act as crosslinking agents include, for example, divinylbenzene, trivinylcyclohexane, trivinylbenzene, 2,2
3,5,6-tetrachloro-1,4-divinylbenzene, esters of unsaturated acids and unsaturated alcohols, such as vinyl crotonate, allyl methacrylate, allyl crotonate, esters of unsaturated acids and polyfunctional alcohols,
For example, trimethylolpropane trimethacrylate, neopentyl glycol dimethacrylate, butanediol dimethacrylate, pentaerythritol triacrylate, tetraethylene glycol diacrylate, triethylene glycol diacrylate, esters of unsaturated alcohols and polyfunctional acids, such as diallyl phthalate, And unsaturated polyethers such as triethylene glycol-divinyl ether and tetraallyloxyethane.

The copolymers used according to the invention may be oxyalkylene groups such as those of the formula (III) of US Pat.
And non-ionic monomers containing oxyethylene groups, such as those represented by

The novel crosslinked ion addition copolymers particularly suitable for use according to the present invention are (1) acrylic and / or
At most 1 repeating unit which is an aliphatic acrylate group
9 mol%, (2) a repeating unit which is an acrylic and / or methacrylic acid base;
And optionally in combination with said unit in the form of a free acid
Many repeat units that Te be 30 mol%, (3) a polyfunctional ethylenically unsaturated addition polymerizable cross-linking monomer
1 to 10 mol% of a repeating unit in the form of a carboxylic acid , and (4) a carboxylate salt originally present in the repeating unit of the copolymer
Reaction with propane sultone or butane sultone
Units containing sulfonate groups obtained by
Crosslinking addition characterized by comprising 50 mol%
It is a copolymer.

The preferred ionically crosslinked addition copolymers for use in accordance with the invention comprise at most 30 mol% of an alkali metal acrylate and / or an onium base (optionally some of said groups are converted to free acid groups). Yes), at most 1
9 mole% of acrylate alkyl ester units such as methyl ester units, tetraallyloxyethane as polyfunctional crosslinking monomer from 1 to 10 mol%, and at least 50 mole% of the groups -COO - (CH _{2) n} - SO ₃ ^- · M ⁺ (n in the formula is 3 or 4, M ⁺ is a cation selected from the group consisting of alkali metal cations and onium groups such as ammonium) comprising repeating units connected to the polymer backbone .
Conversion of the base to the free acid group is effected by acidification in an aqueous medium using, for example, HCl.

The ionic crosslinked copolymer used according to the invention can be made by the following steps:

(1) Emulsion polymerization of an addition-polymerizable aliphatic ester monomer such as methyl acrylate in the presence of an addition-polymerizable polyfunctional monomer such as tetraallyloxyethane.

(2) conversion of at least a part of the ester group in the alkali metal carboxylate group by saponification,

Conversion of at least a portion of the carboxylate groups with propane sultone and / or butane sultone to form a sulphonate group.

For the preparation of special crosslinked addition copolymers containing carboxylic acid groups which can act in the formation of sulfonate groups according to the process described above, US Pat.
0 and 4677050.

A copolymer having a molecular weight of 500,000 or more can be obtained by emulsion polymerization, and the average particle size of the obtained polymer particles in a dispersed form (latex) is 150.
smaller than nm.

In order to demonstrate the synthesis of ionic crosslinked copolymers useful as antistatic agents in hydrophilic colloid coatings of recording materials according to the present invention, the following Preparation Examples I, II, III and
The IV is shown in detail.

Preparation Example I relates to the preparation of an acrylate ester copolymer. Preparation II relates to the partial saponification of the acrylate copolymer to the corresponding potassium salt.

Preparation III involves the partial conversion of the potassium salt to the free carboxylic acid by adjusting the pH to 7.
The obtained copolymer is used in the comparative test shown in Example 2.

Preparation IV relates to the preparation of the potassium sulphonate copolymer according to the invention which is derived from the copolymer of Preparation II via Preparation III.

PREPARATION EXAMPLES I AND II I. Poly ([cl.] Tetraallyloxyethane-co-methyl acrylate) (3/97 molar ratio)

In a 300 l glass lined reaction vessel equipped with a reflux condenser, two inlet openings and a hot water heating jacket, 900 g of DO dissolved in 159 l of deionized water
WFAX 2A1 (DOW Chemica for mixtures of emulsifiers dodecylated oxydibenzene disodium sulfonate and disulfonated dodecyl diphenyl oxide)
ls trademark) was introduced with gentle stirring.

Before introducing into the reaction vessel, 41.2 kg
3.77 kg of (479 mol) methyl methacrylate
(14.8 mol) of distilled tetraallyloxyethane.

Similarly, prior to introduction into the reaction vessel, a separate initiator solution was prepared by dissolving 225 g of potassium persulfate in 16 l of deionized water.

At a reaction temperature in the range of 70-75 ° C., 1/10 of the monomer solution and 1/10 of the initiator solution were introduced into the emulsifier solution in 5-10 minutes with rapid stirring.

A slight exothermic reaction was observed in the course of 15 minutes . Then, the remaining monomer mixture and the initiator solution were gradually added in one hour . This allowed the reaction temperature to reach a maximum of 88 ° C. and a regular reflux of the methyl acrylate was obtained.
After the introduction of the monomer mixture and the initiator solution was completed, stirring was continued for 1 hour . During this time, the reaction temperature dropped to about 80 ° C. Then the reaction mixture was cooled to 25-30 ° C.

About 220 Kg of a latex containing 21 g of crosslinked copolymer in 100 g of dispersion were obtained.
Latex particles had an average particle size of 90-130 nm. The pH of the latex was in the range of 2.5-3 and the viscosity was 2.5 mPa · s at 25 ° C.

II. Poly ([cl] tetraallyloxyethane-co-methyl acrylate / potassium acrylate) (3/18/79 molar ratio)

Into an 80 liter stainless steel reactor equipped with a reflux condenser and a 20 liter dropping funnel, 37.9 kg of the latex prepared above (about 8 ml of polymerized methyl acrylate).
(Including about 7.94 Kg of a copolymer containing 5 moles) and slowly heated to 95 ° C. Next, in water (50% by weight
8.1888 kg of sodium hydroxide) were added over 30 minutes. During the introduction of the potassium hydroxide solution, the temperature of the saponification mixture was maintained at about 95 ° C., and a carefully controlled heating maintained a weak reflux of methanol, thereby eliminating foaming.

The saponification mixture was boiled for a further 8 hours and the boiling point dropped from 100 ° C. to 98 ° C. After cooling, the reaction mixture was filtered through quantitative rapid filter paper.

Poly ([cl.] Tetraallyloxyethane-co-methyl acrylate / potassium acrylate /
Acrylic acid) (3 / 16.8 / 60.2 / 20 molar ratio)

The filtrate obtained in Preparation Example II was neutralized to pH 7.0 by addition of the required amount of LEWATIT S100 ion exchange resin (trademark of BAYER AG, a sulfonated styrene divinylbenzene copolymer in acidic form). After filtering through a filter cloth and adding an appropriate amount of deionized water (pH 7) to remove the ion exchange resin, the copolymer 14.77 was obtained.
A latex having a percentage by weight was obtained. The latex 1K
g., 95.207 g (0.8655 mol) of potassium acrylate units, 20.754 g (0.2882 mol) of acrylic acid units, 20.768 g (0.2415 mol)
Mol) unsaponifiable methyl acrylate units and 10.9
There were 147.7 g of a dry copolymer containing 59 g (0.0431 mol) of tetraallyloxyethane units. This latex copolymer (average particle size: 102.8 μm)
m) is referred to as the K ⁺ polymer.

Production Example IV III. Poly ([cl.] Tetraallyloxyethane-
(Co-methyl acrylate / potassium acrylate / 4-sulfo-butyl acrylate)

[0047]

Embedded image

W = 54.75 mol% y = 16.8 mol% x = 25.45 mol% z = 3 mol%

In a 10 l double wall glass reactor equipped with two dropping funnels, stirrer, reflux condenser, thermometer and pH meter with electrodes in the reactor, 1096.1
7421.4 g of the latex made as described above (Preparation Example III) containing 4 g of K ⁺ polymer were introduced. The dispersion was heated to 75 ° C by flowing 75 ° C water through the double wall structure of the reactor.

1593.75 g in one dropping funnel
(11.704 moles) of butane sultone and another dropping funnel with 1955.4 g of potassium hydroxide 26.7.
A weight percent aqueous solution was charged.

The latex in the reactor is heated at 75 ° C. for about 47
7 g of the above-mentioned aqueous potassium hydroxide solution was added, and the pH was adjusted to 11.0.
I made it. By operating this method, the still free carboxylic acid groups of the K ⁺ polymer were quantitatively converted to potassium carboxylate groups. The total amount of potassium carboxylate in the dispersion is 8.56
It was 23 moles.

While stirring, the butane sultone kept at room temperature in a dropping funnel at 75 ° C. was added to the latex at a rate of 13 g / min. Two hours later, the whole amount of butane sultone was added,
This lowered the pH to 6.16.

The pH was raised again to 7.0 by addition of 264 g of the aqueous potassium hydroxide solution.

After 2 hours and 40 minutes, the pH had dropped again to about 6.21 . Then, about 270 g of the aqueous potassium hydroxide solution was added to adjust the pH to 7.0. This operation was repeated three times in the subsequent reaction course . That is, after a reaction time of 3 hours 30 minutes using about 190.1 g of the solution, 4 hours 15 minutes using about 160 g of the solution, and 5 hours after using about 219 g of the aqueous potassium hydroxide solution, the pH was increased. This raised it to 8.05. A reaction temperature of 75 ° C. was maintained for 20 hours, then cold tap water was circulated through the double wall of the reactor to bring the reactor contents to room temperature. During this time, the pH in the reactor dropped to 5.16 . Subsequently, 374.8 g of the potassium hydroxide aqueous solution was added to raise the pH to about 11.0.

While stirring the dispersion thus obtained,
Injected into 9.5 l of methanol. A fine white powder of poly ([cl.] Tetraallyloxyethane-co-methyl acrylate / potassium acrylate / 4-sulfo-butyl acrylate) was isolated.

After a one hour ramp, the copolymer was filtered off and again stirred in a mixture of 1.06 l of deionized water and 6.00 l of water. The powder is again filtered off, initially under reduced pressure obtained with a water jet pump, and finally at a lower pressure (1 mmHg)
And dried at 50 ° C. to remove water.

Yield of copolymer: 2004.8 g.

Analysis revealed that the copolymer was poly ([c.
l. ] Tetraallyloxyethane-co-methyl acrylate / potassium acrylate / 4-sulfo-butyl acrylate potassium) (3.0 / 16.8 / 25.45 / 5)
(4.75 mole ratio).

For use as an antistatic agent, 200
4.8 g of the dry powder were first dispersed in 11.360 kg of deionized water. P which became 10.0 after 12 hours
H was adjusted to neutral (pH 7) by adding hydrochloric acid. 13.573 kg of copolymer dispersion having 1.979 kg of dry copolymer was obtained . The latex particles are 131.4.
It had an average particle size of nm.

By the addition of hydrochloric acid, part of the potassium acrylate units is converted to acrylic acid units, whereby the composition of the copolymer becomes poly ([cl] tetraallyloxyethane-co-methyl acrylate / Potassium acrylate / acrylic acid / 4-sulfo-butyl acrylate potassium) (3.0 / 16.8 / 19.1 / 6.35 / 5)
(4.75 mole ratio).

FIG. 1 shows various pH values of the hydrophilic colloid layer containing the ion-crosslinked sulfonate copolymer according to the present invention.
Good antistatic properties under conditions are shown as compared to the ionically crosslinked carboxylate polymer from which the sulfonate copolymer was derived. Graphs 1 and 2 in FIG. 1 show a gelatin layer containing a crosslinked carboxylate copolymer prepared according to Preparation Example II (curve 1) and a crosslinked sulfonate copolymer derived therefrom prepared according to Preparation Example IV (curve 2), respectively. The surface resistivity, expressed as logR _s vs. pH, is shown. The gelatin / copolymer weight ratio was 30/70 in the layer applied to the primed polyethylene terephthalate support at a dry coating thickness of 4.0 μm. After hardening the gelatin under the same conditions, each coated and dried material was divided into several pieces, and a pair of pieces of each material was brought to pH from liquid to liquid by one.
Each was immersed in different deionized water solutions that were changed by increasing the pH. The immersed material was dried and measured at 20 ° C. and 30 relative humidity (RH) before measuring the surface resistivity.
Conditioned for 5 hours.

FIG. 2 shows that the surface resistivity (log R _s ) of the gelatin layer containing the sulfonated cross-linked copolymer is plotted against the increase in the conversion (in mol%) of carboxylate groups to sulfoalkyl acrylate groups. The plotted graph is shown. The pre-conversion copolymer contained 80 mol% of carboxylate repeating units. The surface resistivity measurement is performed as follows.
Performed on gelatin layers provided with different sulfonated copolymers on gelatin at a weight coverage of 8 g / m ² versus 0.56 g / m ² . These copolymer / gelatin layers contained 3 g / g
It was coated with hardened gelatin layers having a coating weight of formaldehyde gelatin and 0.0424g / m ² of m ^2. Curing was performed at 57 ° C. and 34% relative humidity for 3 days. Prior to performing the surface resistivity measurements, the layers were treated with an alkaline developer solution, an acidic fixer (pH 4.3) and neutral tap water having a total hardness of 130 ppm calcium carbonate in water. After the treatment, the layer was dried.
21 ° C., 30% relative humidity (R.
H. ) For 15 hours.

The surface resistance in ohms / sq was measured by the following test method:

Two electrically conductive copper poles having a length of 10 cm parallel to each other are placed at 1 cm intervals on the surface to be tested and the resistance formed between the electrodes is measured with a precision ohmmeter. Multiply the measured ohm value by 10 and
Obtain the surface resistance value expressed as ohm / sq.

The cross-linked sulfonated latex-like copolymer for use according to the present invention may be a protein colloid such as gelatin, polysaccharide, polyvinyl alcohol, polyacrylamide and poly-N-vinylpyrrolidone (use of a mixture of said hydrophilic colloids). ) Containing an aqueous hydrophilic colloid solution. The most preferred binder for these medium photographic silver halide emulsion layers is gelatin.

Layers having good antistatic properties even after the wet processing used for photographic silver halide emulsion materials are:
Obtained by coating the sulphonated cross-linked copolymer at a coverage in the range of 6~3g / m ^2.

A hydrophilic colloid binder, for example a 50/50 weight ratio to gelatin and at least 1.6 g / m 2
Coating amount of the copolymer of ² , the total hardness is 130 ppm in water
Ca, M present in tap water equivalent to calcium carbonate
An antistatic layer can be produced which is very good at withstanding the conductivity lowering action of g and Al cations. When the antistatic layer is coated with a fully cured gelatin layer, the effect of the conductivity reduction of the cation is further reduced.

The upper limit of the copolymer coating amount is practically limited by physical properties rather than the conductivity of the antistatic layer. For example, a silver halide emulsion film containing an outermost antistatic layer in which the cross-linked sulfonated copolymer is mixed in a hydrophilic colloid binder in an amount of more than 3 g / m ² has too low scratch resistance and too high water absorption. , Exhibiting poor dimensional stability, and therefore, for use in silver halide films, the coverage is preferably kept below that value.

A preferred recording material according to the present invention comprises one or more photosensitive silver halide emulsion layers, wherein said antistatic layer comprises: (1) the silver halide emulsion layer side of said photographic silver halide emulsion layer material And / or (2) as a backing layer on the side of the support opposite the silver halide emulsion layer of the photographic silver halide emulsion layer material, and / or (3) the photographic halogenation It is present as a silver halide emulsion layer assembly of the silver emulsion layer material or as a layer between the silver halide emulsion layer and the support.

According to a first embodiment, the crosslinked sulfonate copolymer is prepared from an aqueous dispersion on a resin support at a coverage of at least 1.6 to 2.2 g / m ² of dry copolymer. coated, it is coated with obtained layers gelatin cover layer cured at a coverage of 2.0~5.0g / m ^2. Such a layer assembly acts, for example, as a backing layer for a photographic silver halide emulsion layer material. With the above layer assembly, the photographic material was dried following imagewise exposed photographic silver halide emulsion layer material following treatment with an aqueous acidic liquid applied after development, such as an aqueous acidic fix stop bath. Even at times, good antistatic properties are obtained and said properties are maintained.
Said cover layer of hardened gelatin provides the material thus coated with sufficient protection against mechanical damage during handling in photographic processing equipment and transporting the rollers.

According to a second embodiment, the crosslinked sulfonate copolymer is 70/3 based on the hydrophilic colloid binder.
A coating of at least 2.2 g / m ² in a mixture with a hydrophilic colloid binder in a weight ratio of 0 to 80/20 on a resin support , said layer being a photographic silver halide emulsion layer Place in direct contact with the gelatin-silver halide emulsion layer of the material.

The gelatin silver halide emulsion layer may be coated with an abrasion-resistant layer based on hardened gelatin. The surface resistance of such materials can be determined by pre-treating said materials with an acidic aqueous fixer for silver halide (pH 5.0 or less) and even at 30% relative humidity, even when washed with tap water. It is low enough to prevent suction.

According to the present inventors, an antistatic layer having a surface resistivity corresponding to a log R _s value equal to or less than 11.5 is an electrostatic dust layer measured by a test as described in Example 1. It has been found that it gives no properties or very little electrostatic dust suction properties.

According to a third embodiment, the layer coated from the latex containing the crosslinked sulfonate copolymer in the absence of a hydrophilic colloid binder comprises the silver halide of the photographic silver halide emulsion layer material It is provided as an antistatic layer between the emulsion layer and the resin support.

The coating composition for the antistatic layer containing the crosslinked sulfonate copolymer contains other components such as ionic and nonionic surfactants such as a polyoxyethylene compound for improving electric conductivity, a wetting agent as a coating aid, For example, it can contain perfluorinated surfactants, matting agents, pigments and dyes.

According to a particularly preferred embodiment, the antistatic layer containing the crosslinked sulfonate copolymer comprises a colloidal silica or a colloidal silica layer as described, for example, in US Pat. No. 3,525,621 and published European patent application 0 334 400 A1. Use in combination.

The web or sheet according to the present invention may incorporate one or more antistatic layers, each containing an ionically crosslinked latex type copolymer as defined herein. For example, there can be one such antistatic layer on each side of a hydrophobic resin support or resin coated paper. In that way a particularly high resistance to dust suction and spark generation can be achieved.

As mentioned above, in a particular embodiment,
The antistatic layer is covered with a thin protective layer, for example based on hardened gelatin. Suitable hardeners for gelatin include aldehyde hardeners such as formaldehyde, N-methylol compounds, quinones, carboxylic and carbamic acid derivatives, sulfonate esters and sulfonyl halides,
Halogen compounds, epoxides, aziridine, olefins, isocyanates, carbodiimides, isoxazoline salts and vinylsulfonyl compounds such as US-P4845
024 and U.S. Pat. No. 4,894,324. Preferred vinylsulfonyl compound is _{CH 2 = CH-SO 2 -CH} 2 -SO 2 -CH = CH 2. A search for suitable hardeners is available, for example, from Macmillan Publ.
Co. 1977, TH James, The Theory
of the Photographic Process, pages 79-84.

A preferred protective layer is made of gelatin which has been hardened to an extent corresponding to the addition of 0.03 g of formaldehyde per gram of gelatin. The gelatin coverage of the protective layer is preferably 3 g / m ² or less, and is preferably 1 to ² g / m ^2.
The range of m ² is more preferred.

In the form of a mixture with hardened gelatin, the protective layer may comprise a friction-reducing substance such as wax particles (carnauba wax or montan wax), or polyethylene particles,
It may contain fluorinated polymer particles, silicon polymer particles and / or calcium complexing agents.

A common support for photographic silver halide emulsion materials is a hydrophobic resin support or a hydrophobic resin-coated paper support.

[0082] Hydrophobic resin supports are well known to those skilled in the art and are made, for example, from polyester, polystyrene, polyvinyl chloride, polycarbonate . Preferred is polyethylene terephthalate. Preferred resin coated paper supports include poly-α-olefin coated paper supports, such as polyethylene coated paper supports.

The hydrophobic resin support may be provided with one or more subbing layers known to those skilled in the art for adhering a hydrophilic colloid layer thereto. Suitable subbing layers for polyethylene terephthalate supports are, for example, US-P 3,397,988,
It is described in U.S. Pat. Nos. 3,649,336, 4,123,278 and 4,478,907.

Polyester films, such as polyethylene terephthalate films, are usually made by a method in which the film is molecularly oriented by stretching in two mutually direct directions. This method is conveniently accomplished by first stretching a flat amorphous polyester film in one direction and then sequentially in a direction perpendicular thereto. Generally, the film is first stretched in the longitudinal direction, i.e., in the direction of the path through the stretching machine, and then in the transverse direction. The stretched film can be dimensionally stabilized by heat setting under dimensional restraint. Stretching and heat setting are conveniently effected by heating the film above ambient temperature.

When a stretchable resin support, such as a polyethylene terephthalate resin support, is used, the coating of the ionic cross-linked copolymer dispersed in the dissolved hydrophilic colloid binder from the aqueous medium can be in the longitudinal and transverse directions. It is preferable to apply it to such a support after stretching. The stretching is usually 8
It is performed at a temperature in the range of 0 to 100 ° C. The stretched film is treated for 18 to 0.1 minutes while preventing it from shrinking.
Usually, heat setting is performed by heating in the range of 0 to 200 ° C.

The coating of the antistatic layer composition on the support comprises:
Coating methods known to those skilled in the art for gelatin coating can be performed, for example, by doctor blade coating, air knife coating, curtain coating, slide hopper coating or meniscus coating . These are coating methods known from the manufacture of photographic silver halide emulsion layer materials.

Regarding the composition of the silver halide emulsion layer to which the antistatic layer can be provided, for example, Research Disclosure
17643 and Research Disclosu in December 1978
re 307105 in November 1989.

The photographic silver halide emulsion material containing the antistatic layer according to the present invention can be of any type known to those skilled in the art. For example, antistatic layers are useful in continuous tone or halftone photography, micro photography and radiography as well as black as well as color photographic materials.

In a particular embodiment of the invention, a halogen is provided on the back side of the support (opposite side of the photosensitive layer) which is provided with an antihalation layer containing one or more pigments in the form of a mixture with a binder. Use silver halide photographic material . Then, the antistatic layer is provided thereon or between the support and the anti-halation layer. The antireflective material used in the antihalation coating, for example carbon black, can itself have antistatic properties. According to another embodiment, the antistatic layer comprises:
Dyeing with an anti-halation dye which can be removed during processing, for example by an alkaline treatment or a solvent or solvent mixture.

Apart from its use in photographic silver halide emulsion materials, the antistatic layer described above can be used, for example, in Angew.
m. International edition of English, Volume 22 (1983), 191-209
It can be present in a non-photosensitive recording material acting as an image receiving material in a silver complex salt diffusion transfer method or a dye diffusion transfer method as described on page.

The antistatic layer according to the invention is likewise useful for reducing the surface resistance of non-photosensitive adhesive or drafting films which can also be considered as recording materials.

[0092] By using a recording material having an antistatic layer according to the present invention, it can be avoided a problem that is caused by a wet process before or after processing electrostatic charge, or can be substantially reduced. This can be due, for example, to the formation of an electrostatic charge by contact of the back side of the recording material with the silver halide emulsion layer side, or of rubber and hydrophobic polymer binders such as X
The formation of static charges caused by friction with substances such as binder components of phosphor screens used as line intensifying screens means that the use of the antistatic layer of the present invention can be significantly reduced. For example, during loading of a film into a cassette, for example an X-ray cassette, or a camera,
Alternatively, the accumulation of static charge during image handling or projection, as occurs in automatic cameras or film projectors, and thus dust inhalation and / or sparking is prevented.

The examples below are directed to the use of an antistatic layer in combination with a polyethylene terephthalate resin support, for example, a cellulose ester such as polystyrene, polyvinyl chloride, cellulose triacetate or a corona-discharge treated or treated. Other resin substrates made from polyethylene uncoated and / or primed with a subbing layer to improve the adhesion of the hydrophilic colloid layer also exhibit a significant reduction in surface resistance when coated with the antistatic layer described herein. obtain.

The following examples illustrate, but do not limit, the invention. Percentages and ratios are by weight unless otherwise specified.

Example 1 An undercoated polyethylene terephthalate support having a thickness of 175 μm was coated with antistatic layers A, B, C, D and E, respectively, as described below. The dried antistatic layer was coated with a protective hardened gelatin layer as described below.

Production of Comparative Antistatic Material A

For the preparation of the antistatic layer composition A, the following components were mixed at 38 ° C .:

For 100 g of the dispersion (latex),
40 ml of a dispersion containing 14.77 g of the crosslinked carboxylate copolymer (K ⁺ polymer) prepared according to Preparation Example III
20.7 ml of a 10% aqueous gelatin solution, 3.6 ml of a 4% aqueous formaldehyde solution, 1.5 ml of a 5% aqueous solution of a surfactant S1 as described later, and 1N for adjusting the pH to 7.
Sodium hydroxide aqueous solution, coating composition 100m in total
Additional deionized water to l.

While maintaining the temperature at 30 ° C.,
The above-mentioned primed polyethylene terephthalate support was coated with a doctor blade on a hollow metal-coated platen kept at a constant temperature under flowing water having a temperature of 8 ° C. The wet coating thickness was 27 μm.

Cooling platen immediately after coating The platen was cooled with tap water.
The gelatin in the coating layer was fixed. The solid layer obtained after fixing was dried at 40 ° C. in an exhaust dryer cabinet for 10 minutes. The dried layer had a coverage of 2.16 g / m ^2.

For the production of the hardened gelatin coating layer A,
The following components were mixed at 38 ° C.

60 ml of a 10% aqueous gelatin solution, 2.7 ml of a 4% aqueous formaldehyde solution, 1.5 ml of a 5% aqueous solution of a surfactant S1 as described later, a 1N aqueous sodium hydroxide solution for adjusting the pH to 7, and a coating composition were prepared. Additional deionized water to make a total of 100 ml, surfactant S
1 is octyl-phenylene- (OCH ₂ CH ₂ ) ₈ —O—CH ₂
—COOH.

While holding the undercoated polyethylene terephthalate support in contact with the above-mentioned coated platen maintained at a constant temperature by flowing water at 38 ° C., the coating composition kept at 38 ° C. was placed on the dried antistatic layer by a doctor. Coated with blade. The wet coating thickness was 40 μm.

Immediately after coating, the coated platen was cooled with tap water to fix the gelatin in the coated layer (ie, gelled).
The solid layer obtained after fixing was dried in an exhaust dryer cabinet at 40 ° C. for 10 minutes. The dried layer was 3.0 g / m ²
The coating amount was as follows.

The preparation of antistatic materials B, C, D and E was carried out as described for material A, except that a sulfonated crosslinked latex copolymer prepared according to Preparation Example IV and a The other components shown in Table 1 were used in the amounts (ml) shown in the table. 14.5 in 100 g of dispersion
8 g of the copolymer were present.

For each latex composition, the copolymer content was 15.26% in the preparation of Comparative Material A.

The antistatic layer was coated with a hardened gelatin layer of different layer thickness and different composition as shown in Table 2.

Before conducting the surface resistivity measurement, materials A, B,
C and D are used to complete the hardening reaction in gelatin,
It was kept in a humidified cabinet at 57 ° C. for 3 days at a relative humidity (RH) of 4%. The material was then kept at 30% relative humidity (RH) at 21 ° C. for 15 hours.

The surface resistivity (R _s ) was measured using the electrode set as described above, and expressed as a logarithmic value (logR _s ) in ohm / square.

The surface resistivity was measured by measuring the above-mentioned antistatic material A,
For B, C, D and E, they were treated with an aqueous processing solution used for silver halide photography, dried, and then conditioned again at 21 ° C. for 15 hours in an atmosphere of 30% relative humidity.

Table 3 shows the logR _s of the antistatic material constituted as shown in Table 2 before and after the treatment.

Before and after treatment, the antistatic material was subjected to a dust suction test (DAT) . This was done after conditioning the material for 15 hours at 30% relative humidity and 21 ° C. To carry out the test, the materials were placed with their supports on a glass plate and the antistatic layer side was rubbed with a wool cloth. After the rub, cigarette ash was dropped on the surface. In Table 3, the material in which dust remained was indicated by "+", and the material having no dust was indicated by "-".

Table 1 Antistatic coating compositions referred to as B, C, D and E Reference Latex Gelatin Surfactant Hardened layer thickness Preparation Example IV Solution Solution Solution Wet Dry number (ml) (ml) ( Ml ) (ml) (μm) (μm) B 40.61 20.7 1.5 3.61 27 2.21 C 45.74 20.7 1.5 3.93 27 2.36 D 50.87 20.7 1.5 4.27 27 2.57 E 55.90 20.7 1.5 4.60 27 2.76

The pH of each coating composition was adjusted to 7 by adding a 1N aqueous sodium hydroxide solution, and then the volume of each coating composition was made up to 100 ml by adding deionized water.

[0115] Table thickness of 2 material Sosan gelatin surfactant hardening layer Therban soluble liquid soluble liquid solvent liquid wet dry charge No. (ml) (ml) (ml ) (μm) (μm) B1 B 40 1.5 1.8 50 2.0 B2 B 67 1.5 3.0 75 5.0 C1 C 60 1.5 2.7 50 3.0 C2 C 67 1.5 3.0 75 5.0 D1 D 60 1.5 2.7 50 3.0 D2 D 67 1.5 3.0 75 5.0 E1 E 60 1.5 2.7 50 3.0 E2 E 67 1.5 3.0 75 5.0

Table 3 Material composition logR _s D. A. T. Antistatic layer copolymer cover layer body / gelatin ratio gelatin processing Processing Processing Processing charge ^{(g / m 2) (g} / m 2) before and after the before and after A 1.6 / 0.56 3.0 9.7 13.9 - + B1 1.6 / 0.56 2.0 11.45 11.23--B2 1.6 / 0.56 5.0 11.60 11.80 + + C1 1.8 / 0.56 3.0 11.34 11.45--C2 1.8 / 0.56 5.0 11.60 11.80--D1 2.0 / 0.56 3.0 11.20 11.20--D2 2.0 / 0.56 5.0 11.30 11.10-- E1 2.2 / 0.56 3.0 11.10 11.00--E2 2.2 / 0.56 5.0 11.20 11.00--

The treatment was performed at the temperature and treatment time shown below.
The test was performed using the following developing solution, fixing solution and washing solution.

Composition of developer (pH 10.1)-(35 ° C., 27 seconds). Hydroquinone 30 g / l Potassium sulfite 64 g / l 1-phenyl-3-pyrazolidinone 1.5 g / l Potassium bromide 4 g / l Glutardialdehyde 4.7 g / l The pH was adjusted to 10.1 with a bicarbonate / carbonate buffer.

Composition of fixing solution (pH 4.3)-(34 ° C., 18 seconds). Ammonium thiosulfate 132 g / l Sodium sulfite 10.8 g / l Aluminum sulfate 5.4 g / l The pH was adjusted to 4.3 with an acetic acid / acetate buffer.

Washing was performed for 28 seconds with tap water at a temperature of 27 ° C. Tap water had a total hardness equivalent to 336 ppm calcium carbonate in water.

Example 2 A silver bromoiodide emulsion (2 mol% silver iodide) for use in radiography with an intensifying screen
g, the amount of silver halide equivalent to 190 g of silver nitrate is 1K
g and containing silver halide grains having an average grain size of 1.25 μm. As a stabilizer, 545 mg of 5-methyl-7-
It contained hydroxy-s-triazolo [1,5-a] pyrimidine and 6.5 mg of 1-phenyl-5-mercaptotetrazole.

The emulsion was coated on both sides with an undercoated polyethylene terephthalate support coated on both sides with an antistatic layer indicated by E in Table 1 given a copolymer coverage of 2.2 g / m ² . Before coating each emulsion layer on each dried antistatic layer, a 3.00 g / cured gelatin cover layer was applied.
It was applied at a gelatin coverage of m ² . Hardening is 1g of gelatin
Was carried out by adding 0.03 g of formaldehyde.
On each side of the support, each silver halide emulsion layer contained an amount of silver halide equal to 7 g of silver nitrate per m ² .

Lightning was carried out between blue light emitting CaWO ₄ intensifying screens and the exposed photographic material was processed as described in Example 1.

Before measuring the surface resistivity as described above,
The dried radiographic material is 30 ° C., 30% R.F. H. For 2 hours. The surface resistance expressed by logR _s is 1
1.3.

The treated and conditioned material was tested for dust suction as described above and showed no dust retention by electrostatic suction.

[Brief description of the drawings]

FIG. 1 shows the surface resistivity, expressed as a logarithmic value (logR _s ), versus the pH of a gelatin layer containing a prior art crosslinked carboxylate copolymer and a crosslinked sulfonate copolymer according to the present invention, respectively. The plotted graph is shown.

FIG. 2 shows the surface resistivity (log R _s ) of a gelatin layer containing a sulfonated cross-linked copolymer versus increasing conversion (in mole%) of carboxylate groups to sulfoalkyl acrylate groups. The plotted graph is shown.

[Explanation of symbols]

1 Gelatin layer containing crosslinked carboxylate copolymer 2 Gelatin layer containing crosslinked sulfonate copolymer

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-1-168702 (JP, A) JP-A-62-119147 (JP, A) JP-B-49-36214 (JP, B1) (58) Field (Int.Cl. ⁷ , DB name) C08F 220/38 G03C 1/89 B41M 5/28-5/40 CA, REGISTRY (STN)

Claims (5)

(57) [Claims] 1. A recording material comprising a sheet, ribbon or web support layer mixed with an ionic copolymer provided in the form of an aqueous dispersion giving antistatic properties to the recording material, wherein the ionic copolymer is crosslinked. (1) at most 19 mol% of a repeating unit which is an acrylic and / or methacrylic acid aliphatic ester group, and (2) an acryl and / or methacrylic acid base. (3) 1 to 10 mol% of a repeating unit which is a polyfunctional ethylenically unsaturated addition-polymerizable crosslinkable monomer; and (4) a repeating unit of the copolymer. A recording material comprising at least 50 mol% of a repeating unit containing a sulfonate group obtained through a reaction between a carboxylate group originally present therein and propane sultone or butane sultone. 2. The recording material according to claim 1, wherein the sulfonate group is selected from the group consisting of an alkali metal salt and an onium base. 3. The ionic cross-linking addition copolymer has at most 30 mol% of alkali metal acrylate and / or onium base (optionally some of said groups have been converted to free acid groups). At most 19 mol% of acrylate alkyl ester units, 1 to 10 mol% of tetraallyloxyethane as a polyfunctional crosslinking monomer, and a group —COO— (CH ₂ ) _n bonded to the polymer main chain. -SO 3 - _· ^M + ⁽ⁿ in the formula is 3 or 4, M ⁺ is a cation selected from the group consisting of alkali metal cations and onium group) contain at least 50 mole% of repeating units having a The recording material according to claim 1, wherein: 4. The recording material comprises one or more photosensitive silver halide emulsion layers, wherein the layer containing the ionic copolymer is: (1) the photographic silver halide emulsion layer as an outermost layer; On the side of the silver halide emulsion layer of the material and / or (2) as a backing layer, on the side of the support opposite to the silver halide emulsion layer of the photographic silver halide emulsion layer material and / or (3) the support A silver halide emulsion layer assemblage of the photographic silver halide emulsion layer material or a layer between the silver halide emulsion layer and the silver halide emulsion layer material.
Item recording material. 5. A repeating unit which is (1) at most 19 mol% of an acrylic and / or methacrylic acid aliphatic ester group, and (2) a repeating unit which is an acryl and / or methacrylic acid base, and if desired, a free acid (3) 1 to 10 mol% of a repeating unit which is a polyfunctional ethylenically unsaturated addition-polymerizable crosslinking monomer in combination with the above-mentioned unit in the form of An ionic crosslinked addition copolymer comprising at least 50 mol% of a repeating unit containing a sulfonate group obtained by a reaction between a carboxylic acid group originally present in a repeating unit of the copolymer and propane sultone or butane sultone. .